CN1248550A - Process for preparing titanic schorl phase titanium dioxide nanometer crystal under room temp. - Google Patents
Process for preparing titanic schorl phase titanium dioxide nanometer crystal under room temp. Download PDFInfo
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- CN1248550A CN1248550A CN 99113693 CN99113693A CN1248550A CN 1248550 A CN1248550 A CN 1248550A CN 99113693 CN99113693 CN 99113693 CN 99113693 A CN99113693 A CN 99113693A CN 1248550 A CN1248550 A CN 1248550A
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- titanium dioxide
- rutile phase
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Abstract
The preparation method of rutile phase titanium dioxide nanometer crystal is characterized by that it utilizes titanium tetrachloride as main raw material, adopts inorganic acid to control hydrolysis rate, and uses the processes of precipitation, water-washing, alcohol-washing, and vacuum drying so as to obtain rutile phase titanium oxide whose grain size is 7 nonometers. By changing its technological condition, it can obtain granular and long-columnar nanometer titanium oxide whose grain size is 7-100 nanometers. The outstanding feature of said invented method lies in that the obtained product does not undergo the heat treatment, and is rutile phase under the condition of room temp., and its grain size is small, after dried, it has no need of grinding or needs slightly grinding, the rutile phase nanometer titanium oxide powder mass can be obtained.
Description
The present invention relates to the preparation method of rutile-phase nano titanium oxide, belong to field of fine chemical.Use the nano-titanium oxide of present method preparation not need to be the rutile phase under the room temperature through high temperature or compound modifying agent, the control preparation process condition, can obtain minimum grain size is 7～8 nanometers, and the rutile-phase nano crystalline substance of even grain size.
Nano titanium oxide (TiO
2) be meant the titanium dioxide product of its grain-size less than 100 nanometers.Because its particle is little, specific surface area is big, thereby higher chemically reactive is arranged; As a kind of use Chemicals widely, it also has other some performances: chemical property is stable, acid-alkali-corrosive-resisting, the performance of excellent absorption UV-light.Titanium oxide has three kinds of crystal formations: anatase octahedrite, rutile and brookite, preceding two kinds more common also more commonly used.Red schorl phase titanium dioxide is widely used in aspects such as senior pigment, makeup, and its tinting strength is better than anatase octahedrite, is 8 times of the white pigment lithopone used always.Discover, mix in the pigment and a certain proportion ofly nanocrystallinely can significantly improve its uv-absorbing and performances such as scattering, dispersion and rheology.During titanium oxide low temperature that preparation method commonly used prepares is amorphous or the anatase octahedrite phase, just begins to occur the rutile phase when 600 ℃ of calcinings, all changes the rutile phase time into, and particle diameter has reached micron order.Anatase octahedrite changes rutile into and is irreversible transition mutually, and rutile is stable mutually under the room temperature.By in titanium tetrachloride, adding the method for tin tetrachloride, can prepare titanic schorl phase titanium dioxide nanometer crystal, but wherein contain tindioxide, be not pure titanium dioxide, existing preparation technology is difficult to prepare titanic schorl phase titanium dioxide nanometer crystal.
External general employing titanium alkoxide liquid phase or gas phase hydrolysis method, titanium tetrachloride high-temperature oxidation, titanyl sulfate liquid phase sol method carry out the preparation research of nano-titanium oxide, and have realized suitability for industrialized production.TiCl
4Be a kind of inexpensive, industrial chemicals of being easy to get, with TiCl
4For presoma prepares TiO
2The method of super-fine powder has gas phase hydrolysis method, flame hydrolysis and laser pyrolysis processes, all is high-temperature reaction process, and very high to the corrosion-resistant material requirement of equipment, technical difficulty is bigger.The Degusa P-25 nano-titanium oxide of the external Aerosil explained hereafter that adopts promptly is to be raw material with the titanium tetrachloride, adopts the flame method vapor phase hydrolysis to make.The specific surface area of product is 50 meters
2/ gram, particle diameter is about 30 nanometers, anatase octahedrite and rutile mutually and deposit, both mass ratioes are 80 to 20.Can not produce titanic schorl phase titanium dioxide nanometer crystal with existing processes.
The purpose of this invention is to provide a kind of method and produce the red schorl phase titanium dioxide nano powder, this method technology is simple, constant product quality just can obtain the rutile phase without thermal treatment, can prepare the existing littler rutile-phase nano titanium oxide powder of method of particle diameter ratio.
Preparation method's flow process of the present invention as shown in Figure 1.1 is titanium tetrachloride among the figure, and 2 for water adds mineral acid, and 3 is titanium tetrachloride aqueous solution, and 4 is depositing technology, and 5 is moisture TiO
2, 6 is TiO
2Nanocrystalline.1 and the 2 mixed titanium tetrachloride aqueous solutions that obtain after ice-water bath stirs; Again through intensification, hydrolysis, ageing postprecipitation; Throw out is through decompress filter then, and the flush away chlorion forms moisture TiO
2Final moisture TiO
2Make TiO through vacuum-drying
2Nanocrystalline.
The concrete technological specification of each flow process is commented as follows:
1, the selection of mineral acid: it is acid source that mineral acid can be selected concentrated hydrochloric acid or concentrated nitric acid, adds the acidity that water is regulated in acid, plays the effect of control hydrolysis, and the pH value is between 0-1.
2, the concentration of titanium tetrachloride (chemical pure, purity are 98%): should be controlled at certain scope, as the 0.05-0.5 mol, hydrolysis reaction be carried out with moderate speed, the too fast meeting of hydrolysis rate causes hard aggregation, and the crystalline form of product is inhomogeneous.For titania is uniformly dispersed, add the polymeric surface active agent of 0.05-0.5% (mass percent), used tensio-active agent is that molecular weight is the polyoxyethylene glycol of 1500-20000; Molecular weight is the 2000-10000 polyvinyl alcohol.
3, hydrolysis temperature and time: hydrolysis temperature and time all can influence the pattern of nano-titanium oxide greatly, under the different hydrolysis temperatures, need different hydrolysis times, even with the particle diameter that obtains expecting, as not have hard aggregation nano-powder.General hydrolysis temperature is 40-90 ℃, and the time is 1-5 hour, and is concrete relevant with the concentration of titanium tetrachloride aqueous solution.
4, sedimentary ageing and washing: ageing helps obtaining crystal grain and grows powder preferably, and can improve the yield of powder and help sedimentary separation.Washing is in order to remove chlorion, the serious performance that reduces powder of chlorion meeting.Dehydration of organic solvent is used in the washing back, can reduce reunion.In the washing process, can add some ionogen, be beneficial to sedimentary separation.The present invention selects for use alcohols such as ethanol to dewater as organic solvent.Digestion time became with strength of solution, hydrolysis temperature and time, was generally 8-20 hour.
5, drying: the exsiccant purpose is in order to remove the moisture of precipitation absorption, can to adopt 30-60 ℃ of vacuum-drying, or obtain the rutile-phase nano titanium oxide of different-grain diameter and pattern 400-600 ℃ of following thermal treatment.
6, pulverize: be the rutile phase under the powder room temperature that the present invention obtains, better crystallinity degree is without grinding or grinding slightly and can pulverize.
Fig. 2 is the X-ray diffractogram with the TiOx nano crystalline substance of method provided by the invention preparation, and 4 main peaks 7,8,9,10 correspond respectively to the characteristic diffraction peak that rutile 2 θ equal 27.45 °, 36.09 °, 41.23 ° and 54.32 ° among the figure.
Fig. 3, the 4th is with the transmission electron microscope photo of the granular and long column shape rutile of method provided by the invention preparation.
The preparation method's of a kind of titanic schorl phase titanium dioxide nanometer crystal provided by the invention outstanding characteristics are:
1, preparation technology is simple, and processing parameter is easy to control, is easy to large-scale industrial production.
2, do not need through Overheating Treatment and compound modifying agent, be under the room temperature rutile mutually and the powder particle size of existing other hydrolysis process preparation of the particle diameter ratio of powder little.
3, preparation method provided by the invention, grain morphology and particle diameter can be regulated by processing parameter, can obtain granular and TiOx nano crystalline substance long column shape; The purity height (greater than 99%) of product.
Below by embodiment, further illustrate outstanding feature of the present invention and marked improvement, only be the present invention is described and never limit the present invention.
Embodiment 1:
Concentrated hydrochloric acid is added in the entry, and making pH value of aqueous solution is 0.5, ice-water bath, add titanium tetrachloride again, concentration is 0.3 mol, adds the dispersion agent polyoxyethylene glycol, its molecular weight is 3000, and add-on is thousandth (mass percent is with respect to water), 60 ℃ of hydrolysis 3 hours, ageing 12 hours is filtered, washing back alcohol is washed, vacuum-drying, the particle diameter of powder are 7 nanometers, and powder shows light yellow slightly owing to absorb near-ultraviolet light.X-ray diffraction analysis is the result show, powder is the rutile phase, do not have the diffraction peak of anatase octahedrite, brookite.X-ray diffractogram as shown in Figure 2, grain morphology is as shown in Figure 3.
Embodiment 2:
Add in the entry with concentrated nitric acid, regulating the pH value is 0.8, adds titanium tetrachloride, and concentration is 0.4 mol, do not add dispersion agent, hydrolysis temperature is 90 ℃, and hydrolysis time is 2 hours, and digestion time is 20 hours, filter, 30 ℃ of vacuum-dryings, the diameter of the powder of gained are 15 nanometers, and length is that the long column shape of 70 nanometers is nanocrystalline; Through X-ray diffraction analysis is the rutile phase, its grain morphology as shown in Figure 4, all the other are with embodiment 1.
Embodiment 3:
Add in the entry with concentrated hydrochloric acid, making pH value of aqueous solution is 0 (hydrogen ion concentration is 1 mol), ice-water bath, add titanium tetrachloride again, concentration is 0.08 mol, adds 4/1000ths polyvinyl alcohol (molecular weight is about 5000), hydrolysis temperature is 90 ℃, and hydrolysis time is 4 hours, and digestion time is 12 hours, filter, 40 ℃ of vacuum-dryings, obtaining powder is complicated and confused shape coacervate, calcines 2 hours for 400 ℃, the nanocrystalline particle diameter that obtains is 15 nanometers, even grain size.All the other are with embodiment 1.
Claims (4)
1. the novel method of a preparing titanic schorl phase titanium dioxide nanometer crystal under room temp adopts liquid phase method, through hydrolysis, precipitation, drying and disintegrating process, it is characterized in that:
(1) regulates pH value of aqueous solution between 0～1 with mineral acid;
(2) concentration of titanium tetrachloride aqueous solution is controlled at 0.05～0.5 mol scope;
(3) adopting polymeric surface active agent is dispersion agent, and add-on is 0.05～0.5% (mass percent);
(4) hydrolysis temperature is 40～90 ℃, and the time is 1～5 hour;
(5) the precipitation digestion time is 8～20 hours;
(6) vacuum-drying temperature is 30～60 ℃;
(7) dried powder is without grinding or grinding slightly and can pulverize.
2. by the described preparation method of claim 1, it is characterized in that used mineral acid is concentrated hydrochloric acid, concentrated nitric acid.
3. by the described preparation method of claim 1, it is characterized in that the polymeric surface active agent that uses is polyoxyethylene glycol, molecular weight is 1500～20000; Polyvinyl alcohol, molecular weight are 2000～10000.
4. the method for claim 1 is characterized in that in order to control nanocrystalline particle diameter and the pattern of gained rutile phase oxidation titanium, can be further 400～600 ℃ of following thermal treatments 1～3 hour after the drying.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315731C (en) * | 2002-03-01 | 2007-05-16 | 徐瑞芬 | Method of controlling nano titanium dioxide crystal form and obtained nano titanium dioxide using said method |
| CN100334000C (en) * | 2005-12-07 | 2007-08-29 | 华东师范大学 | Process for preparing rutile-phase nano-titanium dioxide |
| CN100334261C (en) * | 2005-12-01 | 2007-08-29 | 华中师范大学 | Rutile type structure TiO2 single dispersed nano-monocrystal and its synthesis method |
| CN100368301C (en) * | 2005-09-13 | 2008-02-13 | 山东轻工业学院 | Mesoporous nanopowder titanium dioxide bionic synthesis method |
| CN100392023C (en) * | 2005-09-01 | 2008-06-04 | 江苏大学 | Nanometer rutile titania sedimentation for preparing mica titanium nanometer composite material |
| CN101346313A (en) * | 2005-12-27 | 2009-01-14 | 朱马国际公司 | Methods for production of titanium oxide particles, and particles and preparations produced thereby |
| CN101844805A (en) * | 2010-06-08 | 2010-09-29 | 上海工程技术大学 | Method for preparing aqueous high-dispersion nano titanium dioxide |
| CN102211788A (en) * | 2010-04-08 | 2011-10-12 | 德元太阳能科技股份有限公司 | Preparation method of titanium dioxide nano powder and titanium dioxide nano powder prepared by same |
| CN101481249B (en) * | 2009-02-17 | 2011-11-09 | 东华大学 | Preparation of agustite coated red schorl phase titanium dioxide nano composite powder (TiO2@HAp) |
| CN101676215B (en) * | 2008-09-19 | 2012-11-07 | 范莉 | Method for preparing titanium dioxide nanosphere by using synergistic action of hydrochloric acid and macromolecular compound |
| CN103232066A (en) * | 2012-12-31 | 2013-08-07 | 青岛瑞丰气体有限公司 | Preparation method of controllable-phase-change titanium dioxide nano-particles |
| CN114853056A (en) * | 2022-04-25 | 2022-08-05 | 武汉工程大学 | Preparation method of nano-scale titanium dioxide with controllable particle size |
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| CN102992399B (en) * | 2012-12-25 | 2014-10-15 | 济南大学 | Preparation method of rodlike rutile nano TiO2 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5030439A (en) * | 1989-10-17 | 1991-07-09 | Kerr-Mcgee Chemical Corporation | Method for producing particulate titanium oxides |
| RU2102324C1 (en) * | 1996-01-15 | 1998-01-20 | Челябинский филиал Ационерного общества открытого типа Научно-производственная фирма "Пигмент" | Method for producing titanium dioxide |
| CN1076319C (en) * | 1997-03-06 | 2001-12-19 | 西北大学 | Method for preparing nanometre-grade titanium dioxide |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315731C (en) * | 2002-03-01 | 2007-05-16 | 徐瑞芬 | Method of controlling nano titanium dioxide crystal form and obtained nano titanium dioxide using said method |
| CN100392023C (en) * | 2005-09-01 | 2008-06-04 | 江苏大学 | Nanometer rutile titania sedimentation for preparing mica titanium nanometer composite material |
| CN100368301C (en) * | 2005-09-13 | 2008-02-13 | 山东轻工业学院 | Mesoporous nanopowder titanium dioxide bionic synthesis method |
| CN100334261C (en) * | 2005-12-01 | 2007-08-29 | 华中师范大学 | Rutile type structure TiO2 single dispersed nano-monocrystal and its synthesis method |
| CN100334000C (en) * | 2005-12-07 | 2007-08-29 | 华东师范大学 | Process for preparing rutile-phase nano-titanium dioxide |
| CN101346313A (en) * | 2005-12-27 | 2009-01-14 | 朱马国际公司 | Methods for production of titanium oxide particles, and particles and preparations produced thereby |
| CN101676215B (en) * | 2008-09-19 | 2012-11-07 | 范莉 | Method for preparing titanium dioxide nanosphere by using synergistic action of hydrochloric acid and macromolecular compound |
| CN101481249B (en) * | 2009-02-17 | 2011-11-09 | 东华大学 | Preparation of agustite coated red schorl phase titanium dioxide nano composite powder (TiO2@HAp) |
| CN102211788A (en) * | 2010-04-08 | 2011-10-12 | 德元太阳能科技股份有限公司 | Preparation method of titanium dioxide nano powder and titanium dioxide nano powder prepared by same |
| CN102211788B (en) * | 2010-04-08 | 2013-05-01 | 财团法人交大思源基金会 | Preparation method of titanium dioxide nano powder and titanium dioxide nano powder prepared by same |
| CN101844805A (en) * | 2010-06-08 | 2010-09-29 | 上海工程技术大学 | Method for preparing aqueous high-dispersion nano titanium dioxide |
| CN103232066A (en) * | 2012-12-31 | 2013-08-07 | 青岛瑞丰气体有限公司 | Preparation method of controllable-phase-change titanium dioxide nano-particles |
| CN114853056A (en) * | 2022-04-25 | 2022-08-05 | 武汉工程大学 | Preparation method of nano-scale titanium dioxide with controllable particle size |
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| CN1086364C (en) | 2002-06-19 |
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